Conversion of materials



Patented Nov. 21, 1944 CONVERSION OF MATERIALS Jacquelin 1!. Harvey,Jr., Washington, D. 0., and

Robert H- Whlte, In, and Joseph A. Vaughan,

Atlanta, Ga., assitnors of one-half to said Harvey, Jr., and one-half toSouthern Wood Preservin ration of Georgia I Company, East Point, 6a., acorpo- No Drawing. Application December 1, 1943, Serial lie. 512,515

Claims.

The instant invention relates to the production of toxic oils employableas fungicides, insecticides, and for any other service to which toxicoils may be put.

More especially the instant invention relates to the production of toxicoils from mixtures of petroleum fractions characterized by ringstructure content. Among such starting materials may be mentionedmixtures of petroleum fractions characterized by ring structure contentrecovered from petroleum fractions by well known extraction methodsincluding extractive distillation and azeotropic distillation. Also maybe mentioned mixtures of petroleum fractions characterized by ringstructure content as flowing from thermal and/or catalytic treatment ofcertain petroleum fractions which includes petroleum fractions havingring structures induced in the course of thermal and/or catalytictreatment, as for example having ring structures induced in the courseof one or more thermal and/or catalytic treatments of unusual length, asfor example, for periods of from 1-10 hours or more.

An object of the instant invention is the production of toxic oils fromthe aforenamed petroleum fractions or others whereby to provide oils ofthe preservative type. as for example preservative wood impregnantsconforming to specifications extant or acceptable to the trade consumingsuch oil materials.

Another object of the instant invention is the provision of preservativewood impregnants having boiling ranges and residues in accordance withpublished specifications and/or in accordance with consumer preference.

Another object of the instant invention is the reforming, modifying,converting and/or transforming of the mixtures of hydrocarbons wherebyto induce toxicity.

Another object of the instant invention is the unveiling of latenttoxicity in mixtures of petroleum fractions having inherent butinhibited toxicity.

Another object of the instant invention is the coordination of processvariables so as to provide specific gravities within definite limits invarious fractions of the beneficiated material.

Another object of the instant invention is th induction of toxicity inthe presence of catalytic materials adapted to favorably influence saidtoxicity induction.

In the past wood preservative oils of the high temperature coal tarderived type have been employed in quantities greatly exceeding thetotal of all other wood preservative oils. From the standpoint ofavailability of said coal tar as the parent product ofvvood preservativeoils, it is annuall produced in this country under normal conditions tothe extent of five hundred million to six hundred million gallons. Thisquantity of coal tar is capable of yielding an amount of highlyeffective wood preservative oil which would make this country selfsufficient in its wood preservative requirements. However, due to thefact that when a wood preservative distillate (creosote) is recoveredfrom coal tar there remains in the still a residue (pitch) which, atbest, is a low priced product and which, at worst, is a seriouslydistress product to the end that at times it is placed in inventoryrather than sold, the current method of distilling tar leaving much tobe desired. The net result of this situation obtaining is that the coaltar distiller usually confines himself to that distillation recovery ofcreosote which would correspond to the attending amount of pitch that hecan market at a profit. Accordingly, over a period of years severalhundred million gallons of creosote oil have been imported into thiscountry. That such a situation should obtain is apparently a paradox inthat we annually produce a quantity of high temperature coal tar whichif processed to yield creosote would make us self sufficient in thatrequirement. A survey of this paradox is fully outlined in an addressgiven by no less an authority than S. P. Miller, technical director, TheBarrett Company, 40 Rector Street, New York city, before the FranklinInstitute, Philadelphia, Pennsylvania, in December, 1932. The economicsof coal tar have not materially changed since that date.

In view of the apparent inability of the coal tar industry to providenational needs of wood preservative oils, a strong incentive is given togroups processing other types of oil to invade the lucrative woodpreservative market. At the present time many types of aromatic oils areproduced by the petroleum industry, and the high boiling oils ofaromatic content produced by this industry have for several years beentested for their wood preservative efllciency.

By the term "petroleum aromatic" as used herein and in the appendedclaims is meant to include mixtures of petroleum fractions characterizedby cyclic content and include specifically various forms and types ofnaphthenes found in various mixtures of petroleum fractions, as forexample monocyclic-and polycyclic naphthenes.

The so-called petroleum aromatics which includes the monocyclic andpolycyclic naphthenes and unsaturated hydrocarbon fractions have in thepast been produced in very large quantities. However, very little workhas been done on these materials. Such a fact is borne out on page 667,Reactions of pure hydrocarbons" Gustav Eglofl, Reinhold PublishingCorporation, 330 West 42nd Street, New York city, which states:

"Despite the fact that naphthenes or cycloparaiiines are available inenormous quantities. as shown by an estimate of 100.000.000 barrelspresent in the 1,498,000.000 barrels of crude oil which was the world'sproduction in 1934. comparatively little work of a pyrolytic nature hasbeen performed on individual naphthene hydrocarbons or thecycloolefins."

Several oils of cyclic content produced by the petroleum industry havebeen inspected for their toxicity to wood destroying fungi, among whichmay be mentioned a high boiling oil of cyclic content produced (1940) atthe Wood River Refinery of the Shell Oil Company and which has thefollowing inspection:

Gravity 10.8 Flash, P. M. C. C F 295 Flash, 0, O. C F 290 Fixed carbonper cent 4.9 Pour point F 10 B. S. 8: W -per cent by volume 0.1 S. U,vis. 100 F 151 s. U. vis. 210 F 41 s. F, vis. (a) 77 F 34.5 Carbonresidue 6.8 Per cent aromatics and unsaturates 82.4 Sol. in CS: 99.8Loss 50 grams. hours, 325 F 8.9 Residue of 100 pene per cent 37.5 A. S.'I. M. distillation:

I. B. P F 518 10% rec. (d) F 51B rec. F 589 rec. (d "F 614 rec. (17 "F637 rec. "F 660 rec. "F 675 Maximum.

In the foreaoing tabular data P. M. C. 0. means Pensky- Martin ClosedCup: C. O. C. means Cleveland Open Cup.

Upon evaluat n the foregoing oil for its toxicity to wood destroyingfungi (Madison 517), it was found that this oil did not inhibit thegrowth of the fun i named at a concentration of up to and including 10%.

It is now discovered that the oil above named or other oils of cycliccontent produced by the petroleum industry can be increased in toxicityin accordance with the process of the instant invention.

According to the instant invention oils of cyclic content produced bythe petroleum industry are reformed, transformed. modified and/orconverted to oils of a more toxic nature having characteristicsacceptable to consumers of wood preservative impregnant and/orconforming to wood preservative specifications extant.

It is a specific object of the instant invention to reform, transform,modify and/or convert mixtures of petroleum fractions characterized bycyclic structures having inherent but inhibited toxic properties in thevapor phase, with or without catalysts, to materials exhibiting a morepronounced toxicity than the parent feed stock.

In former attempts to provide a wood Preservative oil of petroleumorigin by processes analogous to that of the present invention, the feedstock utilized as starting material or the process adopted, or both,were such as to provide an oil boiling about at 270 C. or in anotherinstance with only 0.8% residual matter at 315 C. These products havenot been found acceptable in the art.

One of the petroleum oils hydroformed in vapor phase above noted had thefollowing distillation range:

Oil, per Distillation cent The oil above named after its impregnationinto cellulosic materials to be preserved is entirely too volatile toprovide an acceptable preservative impregnant.

It is, therefore, an object of the instant invention to provide a vaporphase process which yields a reformed petroleum oil characterized byinduced toxic properties having at least about iii-20% residual matterabove 315 C.

By the expression a reformed petroleum oil" as used herein and in theannexed claims is meant a beneficiated petroleum oil having inducedtoxicity as stemming from, among other things a change in molecularstructure which occurs during the practice of the present process. Thus"a reformed petroleum oil is a modified, converted and/or transformedoil, and includes an oil reformed by substitution, addition and/orsubtraction from the moiecular structure of the feed stock.

We have discovered that some of the mixtures of petroleum fractions havevery substantial residual matters above 355 C. and inherent toxicproperties inhibited by the complexity of the structure, which structureis inherently unstable. Taking advantage of the lack of stability of thecomplex structure of these relatively hiah boiling oils that havesubstantial residual matters above 315 C. or 355 C., we are able bysubjecting them to vapor phase reforming conditions to simplify andstabilize the structure whilst providing in the finally beneficiated oilsubstantial residual materials above 315 C. or 355 C., at the same timeunveiling the toxic qualities. and if the process is carried to anextent to provide specific gravities in fractional parts of thebeneficiated material as noted in the following tabular data:

Fractions Low limit High limit 0. 801 l. 0048 0. 850 1. 0315 0. 914 l.0691 0. 973 l. 1175 and preferably carried to the extent to providespecific gravities in fractional parts of the beneflciated material asnoted in the following tabular data:

from the beneflciated material the excess oi fractions boiling below 210C. as required by commercial specifications (or specifically whateverother low boiling temperature is specified), we are able to use theresidue as a commercial wood preservative impregnant with acceptabletoxic properties. In the event this material has too great a residue at355 C. or has too high a coke residue for any particular service thedesired preservative oil may be secured as an extract, distillate orresidue having no excess of the desired materials at 355 C. or an excessof coke residue.

The following examples will illustrate several modes of practicing theprocess of the instant invention.

Example 1.-A so-called petroleum aromatic, relatively non-toxic, havingsubstantially no ends boiling below 270 0., materials boiling at about355 0., specific gravities of 0.9251 and 0.9537 in the fractions 270-315C. and 315-355 0., respectively, is subjected in the vapor phase to atemperature of 500 C. whilst under a pressure of 1,000 pounds for such alength of time as to provide newly formed materials boiling below 210 C.and in fractional parts of the beneficiated oil a specific gravityfalling between the limits noted in the following tabular data:

Fractions Low limit I High limit 2l0-Zi5 C 0.801 1.0048 315-355 C 0. 973i. 1175 and preferably for such a length of time as to provide in thefractional parts of the beneflciated oil a specific gravity fallingbetween the limits noted in the following tabular data:

Fractions i Low limit High limit 21o-2a5c 5 0.820 0.9m 3l5-355 C 1.0011.1025

(Madison 51'?) than the parent feed stock to such 55 an extent as to beuseful as wood preservative. The induction and/or provision of thespecific gravities in the fractional partsof the beneficiated oilmentioned above is a valid test for the induction of toxicity in thefractions referred to, and further is an indication that toxicity hasbeen induced in other fractions of the material under treatment.

The overall beneficiated material may be used as a preservative or forany other purpose to which toxic oils are put. If desired. a woodpreservative impregnant complying with specifications extant or ofconsumer preference,-may be segregated from the overall beneflciated oilas a stabilized residual, distillate or extract, and in the event theextract has non-permissible low boiling ends, the extract may bestabilized to the desired extent by removal of low boiling ends.

As illustrative of wood preservative impregnants that are meeting withconsumer acceptonce and which may be segregated from the overallbeneficiated material of the instant process. the following tabular datashow several published specifications:

Woon Pamaava'rrvs Imrnmnm'rs Specifications 1. American Wood Preservers'Association it. Up to 210 0., not more than 5% 1). Up to 235 0., notmore than 25% 2. American Wood Preservers' Association a. Up to 210 0.,not mor than 1% b. Up to 235 0., not more than 10% 0. Up to 355 0., notless than 65% 3. American Wood Preservers' Association a. Up to 235 0.,not more than 0. Up to 300 0., not more than 16%% c. Up to 355 0., notless than 45% 4. American Wood Preservers Association :1. Up to 210 0.,not more than 8% b. Up to 235 0., not more than 35% 5. American WoodPreservers Association a. Up to 210 0., not more than 10% 0. Up to 2350., not more than 40% 6. American Wood Preservers Association 0. Up to210 0., not more than 5% b. Up to 235 0., not more than 15% 7. PrussianRy.

(1. Up to 0., not more than 3% b. Up to 200 0., not more than 10% 0. Upto 235 0., not more than 25% 8. National Paint Varnish 8r LacquerAssociation #220 a. 5% at 162 0. b. 97% at 270 0. 9. Southern pineshingle stain oil a. 5% at, 137 0. b. 95% at 257 C. Neville shinglestain oil a. I. B. P., 150 C. b. 5% at 205 0. c. 95% at 292 0. 11.Carbolineum 270 0., I. B. P.

By the nature of the process it is obvious that modifications ofexisting specifications or other and more exacting specifications may bemet.

As mentioned in the foregoing the process variables are so coordinatedas to jointly provide newly formed fractions boiling below 210 C. and apreferred limit of specific gravities in the fractions 210-235 C. and315-355 C. of the beneficiated oil.

In lieu of jointly controlling the process as to provide the aforenamedspecific gravities in the 210-235 0. and 315-355 0. fractions of thebeneficiated oil, the proper control may be evidenced in accordance withthe following example:

Example 2.-Select a material comparable in chemical analysis and boilingrange to the feed stock mentioned in Example 1. Subject same in vaporphase to a temperature of 505 C. whilst under a pressure of 2,000pounds. Carry on the process for such a length of time as to jointlyprovide (l) newly formed oils boiling below 210 0. and (2) in thefractions 235-270 0. and 315-355" 0. specific gravities falling betweenthe limits noted below:

and preferably between the following limits:

Operating under the conditions above named a period of about one andone-half hours will illus.. tratively serve to provide a. percentage ofnewly induced materials boiling below 210 C. and specific gravitiesfalling between the preferred limits in the fractional parts of thebeneficiated 011 above noted.

At the end of the named treatment period the oil is condensed andinspected, and is found to have induced toxic properties. The inductionof the specific gravities in the fractional parts of the beneficiationstated in the present example is a valid test for the induction oftoxicity in the fractions referred to, and further is an indication thattoxicity has been induced in other fractions of the material undertreatment.

Example 3.Se1ect a material comparable to the feed stock mentioned inExample 1. Subject same in vapor phase to a temperature of 525 C. whilstunder a pressure of 3,000 pounds. Carry on the process for such a lengthof time as to jointly provide and/or induce (1) newly formed oilsboiling below 210 C. and (2) in the fractions 2'70-315 C. and 315-355 C.specific gravities falling between the limits noted below:

and preferably between the following limits:

Fractions Low limit High limit 270-315" C 0. 942 1.0541 3l5-355 C 1. 001l. 1025 Operating under the conditions above named a period selectedbetween the limits of 30 and 40 minutes will illustratively serve toprovide a percentage of newly induced materials boiling below 210 C. andspecific gravities falling between the preferred limits in thefractional parts of the beneflciated oil noted above.

When the period of treatment has been completed the oil is cooled,condensed and inspected. It will be found that the overall beneficiationrequires a smaller concentration for given growth inhibition of wooddestroying fungi than the parent feed stock to such an extent as to beuseful as a wood preservative. The induction of the specific gravitiesin the fractional parts of the beneficiated oil mentioned in the instantexample is a. valid test for the induction of toxicity in the fractionsreferred to, and further is an indication that toxicity has been inducedin other fractions of the material under treatment.

Example 4.-Select a petroleum aromatic extract boiling preponderantlyabove 270 C. and materials boiling at least as high as about 355 C.Subject same in vapor phase to a temperature of 510 C. whilst under apressure of 1500 pounds. Carry on the process for such a length of timeas to jointly provide (1) newly formed oils boiling below 210 C. and (2)in the fraction boilin between 315 C. and 355 C. a specific gravityfalllng between the limits of 0.973 and 1.1175, and

preferably between the limits of 1.001 and 1.1025.

Carrying on the process under the conditions of the instant example aperiod of about on hour and 15 minutes will illustratively serve toprovide a percentage of newly induced materials boiling below 210 C. anda specific gravity falling between the preferred limits in the 315-355C. fraction of the beneflciation.

At the end of the processing period the oil is cooled, condensed andinspected, Find in the beneflciation a toxicity in excess of that of theparent feed stock. The induction of the specific gravity between thelimits stated in the materials boiling between 315 C. and 355 C. is avalid test for the induction of toxicity in the fraction referred to,and further is an indication that toxicity has been induced in otherfractions of the material under treatment.

As noted in the tabular data shown in the foregoin giving boiling rangespecifications for oil wood preservatives, many preservative oils arepossible of segregation from the beneficiated feed stock of inducedtoxicity. As for example, an oil boiling within the carbolineurnpreservative range,

in which instance the segregation would have an initial boiling point ofabout 270 C., the fractions 270-315" C. and 315355 C. of which, wouldhave specific gravities falling between the limits of 0.914-1.0691 and0.973-L11'15, respectively,

Example 5.Practice the process of Example 1 with a molybdenum oxidecatalyst.

Example 6.Practice the process of Example 2 with a chromium oxidecatalyst. Example 7.--Practice the process of Example 3 with a vanadiumoxide catalyst.

Example 8.Practice the process of Example 4 with a tin oxide catalyst.

Example 9.Practice the process of Example 1 with a molybdenum sulfidecatalyst.

Example 10.Practice the process of Example 2 with a chromium sulfidecatalyst.

Example 11.-Practice the process of Example 3 with a vanadium sulfidecatalyst.

Example 12.Practice the process of Example 4 with a tin sulfidecatalyst.

Example 13.--Practice the process of Example 1 with the coprecipitatedoxides of copper and chromium as catalytic materials.

Example 14.Practice the process of Example 2 with tin chloride ascatalytic material.

Example 15,-Practice the process of Example 3 with aluminum chloride ascatalytic material.

Example fit-Practice the process of Example 4 with iodine as catalyticmaterial.

Example 17.-Practice the process of Example 1 with iodoform as catalyticmaterial.

Example 18.Practice the process of Example 2 with hydriodic acid ascatalytic material.

Example 19.Practlce the process of Example 3 with chlorine as catalyticmaterial.

Example 20.--Practice the process of Example 4 with bromine as catalyticmaterial.

Example 21.Practice the process of Example 1 with a hydrogen halid ascatalytic material.

Example 22.--Practice the process of Example 2 with ammonium chloride ascatalytic material.

Example 23.-Practice the process of Example 3 with pelleted bentoniteclay as catalytic materlal.

Example 24.Practice the process of Example 4 with activated Attapulgusclay as catalytic material.

Example 25.Practice the process of Example 1 with a silica hydrogel ascatalytic material.

Example 26.Practice the process of Example 2 with a silica hydrogelimpregnated with an aluminum salt as catalytic material.

Example 27.--Practice the process of'Example 3 with bentonite and anadsorptive clay as catalytlc materials.

Example 28.-Practice the process of Example 4 with a siliceous materialimpregnated with a metallic oxide as catalytic material.

Example 29.-Practice the process of Example 1 with a siliceous materialimpregnated with a metallic sulfide as catalytic material.

Example 30.Practice the process of Example 2 with coprecipitated aluminaand chromia hydrogels as catalytic materials.

Example 31 .--Practice the process of Example 3 with a syntheticsilica-alumina gel as catalytic material.

In the Examples 1-4, inclusive, instances have been cited wherein thestarting feed stocks have very small percentages, if any, of materialsboiling below 270 C. The instant process, as illustrated by Examples 1-4incl sive, or others, is adapted to thermally treat in vapor phase,within the processing limits herein disclosed, a mixture of petroleumfractions characterized by relatively little toxicity, as for examplethe so-called aromatic extracts, having fractions boiling within thewood preservative range and thereby provide an overall treated oilrequiring a smaller concentration for a given growth inhibition of wooddestroying fungi than the starting feed stock to such as extent as to beuseful as a wood preservative impregnant.

Various catalysts assist in the reforming, transforming, modifying and/rconverting of the starting petroleum oils whereby to provide materialsof induced toxic properties. Many catalysts other than noted in theforegoing are also employable as effective substances. Viewed broadly,the oxides and sulfides of metals may be used as well as the carbonatesand metals themselves. Cellulosic materials and carbon, activated orotherwise may be used with advantage. Especially effective as catalyticmaterials are oxides and sulfides of metals, siliceous materials,halids, halogens and derivatives thereof, including specificallysubstitution and addition products thereof, as for example andspecifically substitution and addition products of said derivatives, saya hydrogen halid, employed in Well known manner.

The catalysts employed in the instant process are reforming" catalysts.By the expression a reforming catalyst is meant a catalyst adapted tofavorably influence the reactions that are conducive to the induction oftoxicity, be the reactions those of addition, subtraction orsubstitution.

The temperatures in the instant process may be selected over a widerange dependent upon the pressures employed. It is, of course,understood that when relatively low temperatures are employed the lowerwill be the pressure in order to provide vapor phase operation, and whenoperating at very low temperatures pressures only slightly aboveatmospheric will suffice. Temperatures employable are selected betweenthe limits of 400-600 0., and preferably between 425500 C.

Various pressures are employable as for instance 10, 50, mo atmospheresor higher, and these pi ssures are so coordinated with the temperaturesselected as to give total or substantially total vapor phase operation.

If desired instead of subjecting the entirety of the starting feed stockto a single toxicity inducing operation in the vapor phase, the parentmaterial may be segregated into a plurality of cuts and these pluralityof cuts separately subjected to separate vapor phase toxicity inducingoperations wherein the temperatures in each instance are dissimilar, asfor example, but not as a restriction, subjecting the highest boilingcut to the lowest temperature, etc.

The time element is specifically selected so as to provide in theoverall beneficiated material newly formed materials boiling below 210C. and specific gravities in the fractional parts described fallingbetween the stated limits. Using any given feed stock, a few trials willenable those skilled in the art to determine the correct period oftreatment.

It is to be understood that the treatment periods shown in Examples 1-4are for purposes of illustration only. With some feed stocks the periodof treatment necessary to provide the stated specific gravities infractional parts of the material undergoing treatment may be only a fewminutes. Thus the period of treatment in the instant process may beviewed broadly as that time required to induce (a) newly formedmaterials boiling below 210 C., and (b) specific gravities in fractionalparts of the beneficiation falling between the disclosed limits.

The process of the instant invention may be practiced in an intermittentprocessing vessel or in a continuous manner as will become apparent tothose skilled in the art after having read the foregoing disclosures.

In the examples shown in the foregoing, one or more phases etc. of oneexample may be added to or substituted for other phase or phases inanother example where the substitution or addition is obviouslyworkable.

Minor changes may be made within the scope of the appended claimswithout departing from the spirit of the invention. In the claimsaflixed to this specification no selection of any particularmodification is intended to the exclusion of other modifications thereofand the right to subsequently make claims to any modification notcovered by these claims is expressly reserved.

We claim:

1. In the induction of toxicity into a mixture of petroleum fractionsboiling preponderantly above 270 C., characterized by a substantialpercentage of "petroleum aromatics, and inherent but in-' hibitedtoxicity, the process which comprises:

subjecting said material in vapor phase to a temperature selectedbetween the limits of 400-600 C.; unveiling toxicity in the materialunder treatment by carrying on the process for a period notsubstantially in excess of about one hour. the period being so selectedwith reference to the chosen temperature and pressure as to jointlyprovide newly formed materials boiling below 210 C. and specificgravities in the fractions 210-235 C. and 315-4355" C. of thebeneficiated material, falling between the limits of about 0.801-l.0048and 0.9'i'3-l.l175, respectively; and segregating from the beneficiatedmaterial an oil of the wood preservative type boiling preponderantlybetween 210 C, and 355 C., said oil characterized by induced toxicproperties and at least about 10-20% residual matter above 315 C., thefractions 21!)- 235" C. and 315-355 C. of which have specific gravitiesfalling between the limits above noted.

2. In the induction of toxicity into a mixture of petroleum fractionsboiling preponderantly above 270 0., characterized by a substantialpercentage 01' "petroleum aromatics," and inherent but inhibitedtoxicity, the process which comprises: subjecting said material in vaporphase to a temperature selected between the limits of 400-600" C.;unveiling toxicity in the material under treatment by carrying on theprocess for a period not substantially in excess of about one hour, theperiod being so selected with reference to the chosen temperature andpressure as to jointly provide newly formed materials boiling below 210C. and specific gravities in the fractions 235-270 C. and 315-355 C. ofthe beneilciated material, falling between the limits of about0.850-l.0315 and 0.973-1.11'75, respectively; and segregating from thebeneflciated material an oil of the wood preservative type boilingpreponderantly between 210 C. and 355 C., said oil characterized byinduced toxic properties and at least about 10-20% residual matter above315 C., the fractions 235- 270 C. and 315-355 C. of which have specificgravities falling between the limits above noted.

3. In the induction of toxicity into a mixture of petroleum fractionsboiling preponderantly above 270 C. characterized by a substantialpercentage of petroleum aromatics, and inherent but inhibited toxicity,the process which comprises: subjecting said material in vapor phase toa temperature selected between the limits of 400-600" C.;unveiling-toxicity in the material under treatment by carrying on theprocess for a period not substantially in excess of about one hour, theperiod being so selected with reference to the chosen temperatures andpressure as to jointly provide newly formed materials boiling below 210C. and specific gravities in the fractions 270-315 C. and 315-355 C. ofthe beneflciated material, falling between the limits of about0914-10691 and 0.973-L1175, respectively; and segregating trom thebeneficiated material an oil of the wood preservative type boilingpreponderantly between 210 C. and 365 C., said oil characterized byinduced toxic properties and at least about 10-20% residual matter above315 0., the fractions 270-3l5 C. and 315-355 C. of which have specificgravities falling between the limits above noted.

4. The process of claim 1 with inclusion 0! CERTIFICATE OF CORRECTION.

Patent No. 2, 363 ,2ii5.

carrying on the process in the presence of a reforming catalyst.

5. The process of claim 2 with inclusion of carrying on the process inthe presence or a reforming catalyst.

6. The process or claim 3 with inclusion of carrying on the process inthe presence of a reforming catalyst.

7. The process 01' claim 1 with inclusion of carrying on the process inthe presence oi a catalytic material selected from the group consistingof oxides and sulfides 0! heavy metals.

8. The process of claim 2 with inclusion of carrying on the process inthe presence of a catalytic material selected from the group consistingof oxides and sulfides oi heavy metals.

9. The process of claim 3 with inclusion of carrying on the process inthe presence of a catalytic material selected from the group consistingof oxides and sulfides of heavy metals.

10. The process of claim 1 with inclusion of carrying on the process inthe presence of a halogen, halid or derivative thereof, includinsubstitution and addition products thereof, as catalytic material.

11. The process of claim 2 with inclusion of carrying on the process inthe presence of a halogen, halid or derivative thereof, includingsubstitution and addition products thereof, as catalytic material.

12. The process of claim 3 with inclusion of carrying on the process inthe presence of a halogen, halid or derivative thereof, includingsubstitution and addition products thereof, as catalytic material.

13. The process of claim 1 with inclusion of carrying on the process inthe presence of siliceous material as catalytic agent.

14. The process of claim 2 with inclusion 01' carrying on the process inthe presence of siliceous material as catalytic agent.

15. The process of claim 3 with inclusion or carrying on the process inthe presence of siliceous material as catalytic agent.

JACQUELIN E. HARVEY, Ja. ROBERT H. WHITE, JR. JOSEPH A. VAUGHAN.

November 21, 191 1;.

JACQUELIN E. HARVEY, JR., ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,first column, line 59, for "10% rec. l. 518" read "10% rec. Q F. 565;and that the said Letters Patent should be read with this correctiontherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 20th dayof February, A. D. 191,6.

(Seal) Leslie Frazer "A m. Acting Commissioner of Patents.

270 0., characterized by a substantial percentage 01' "petroleumaromatics," and inherent but inhibited toxicity, the process whichcomprises: subjecting said material in vapor phase to a temperatureselected between the limits of 400-600" C.; unveiling toxicity in thematerial under treatment by carrying on the process for a period notsubstantially in excess of about one hour, the period being so selectedwith reference to the chosen temperature and pressure as to jointlyprovide newly formed materials boiling below 210 C. and specificgravities in the fractions 235-270 C. and 315-355 C. of the beneilciatedmaterial, falling between the limits of about 0.850-l.0315 and0.973-1.11'75, respectively; and segregating from the beneflciatedmaterial an oil of the wood preservative type boiling preponderantlybetween 210 C. and 355 C., said oil characterized by induced toxicproperties and at least about 10-20% residual matter above 315 C., thefractions 235- 270 C. and 315-355 C. of which have specific gravitiesfalling between the limits above noted.

3. In the induction of toxicity into a mixture of petroleum fractionsboiling preponderantly above 270 C. characterized by a substantialpercentage of petroleum aromatics, and inherent but inhibited toxicity,the process which comprises: subjecting said material in vapor phase toa temperature selected between the limits of 400-600" C.;unveiling-toxicity in the material under treatment by carrying on theprocess for a period not substantially in excess of about one hour, theperiod being so selected with reference to the chosen temperatures andpressure as to jointly provide newly formed materials boiling below 210C. and specific gravities in the fractions 270-315 C. and 315-355 C. ofthe beneflciated material, falling between the limits of about0914-10691 and 0.973-L1175, respectively; and segregating trom thebeneficiated material an oil of the wood preservative type boilingpreponderantly between 210 C. and 365 C., said oil characterized byinduced toxic properties and at least about 10-20% residual matter above315 0., the fractions 270-3l5 C. and 315-355 C. of which have specificgravities falling between the limits above noted.

4. The process of claim 1 with inclusion 0! CERTIFICATE OF CORRECTION.

Patent No. 2, 363 ,2ii5.

carrying on the process in the presence of a reforming catalyst.

5. The process of claim 2 with inclusion of carrying on the process inthe presence or a reforming catalyst.

6. The process or claim 3 with inclusion of carrying on the process inthe presence of a reforming catalyst.

7. The process 01' claim 1 with inclusion of carrying on the process inthe presence oi a catalytic material selected from the group consistingof oxides and sulfides 0! heavy metals.

8. The process of claim 2 with inclusion of carrying on the process inthe presence of a catalytic material selected from the group consistingof oxides and sulfides oi heavy metals.

9. The process of claim 3 with inclusion of carrying on the process inthe presence of a catalytic material selected from the group consistingof oxides and sulfides of heavy metals.

10. The process of claim 1 with inclusion of carrying on the process inthe presence of a halogen, halid or derivative thereof, includinsubstitution and addition products thereof, as catalytic material.

11. The process of claim 2 with inclusion of carrying on the process inthe presence of a halogen, halid or derivative thereof, includingsubstitution and addition products thereof, as catalytic material.

12. The process of claim 3 with inclusion of carrying on the process inthe presence of a halogen, halid or derivative thereof, includingsubstitution and addition products thereof, as catalytic material.

13. The process of claim 1 with inclusion of carrying on the process inthe presence of siliceous material as catalytic agent.

14. The process of claim 2 with inclusion 01' carrying on the process inthe presence of siliceous material as catalytic agent.

15. The process of claim 3 with inclusion or carrying on the process inthe presence of siliceous material as catalytic agent.

JACQUELIN E. HARVEY, Ja. ROBERT H. WHITE, JR. JOSEPH A. VAUGHAN.

November 21, 191 1;.

JACQUELIN E. HARVEY, JR., ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,first column, line 59, for "10% rec. l. 518" read "10% rec. Q F. 565;and that the said Letters Patent should be read with this correctiontherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 20th dayof February, A. D. 191,6.

(Seal) Leslie Frazer "A m. Acting Commissioner of Patents.

